Molecular interaction mechanism in the separation of a binary azeotropic system by extractive distillation with ionic liquid

Ionic liquids (ILs) have shown excellent performance in the separation of binary azeotropes through extractive distillation [1]. But the role of the ionic liquid in azeotropic system is not well understood. In this paper, COSMO-RS model was applied to screen an appropriate IL to separate the binary azeotrope of ethyl acetate (EA) and ethanol and 1-octyl-3-methylimidazolium tetrafluoroborate ([OMIM][BF4]) was selected. The Quantum Mechanics (QM) calculations and molecular dynamics (MD) simulation are performed to study the interactions between the solvent molecules and [OMIM][BF4], in order to investigate the separation mechanism at the molecular level. The nature of the interactions is studied through the reduced density gradient (RDG) function and quantum theory of Atom in Molecule (QTAIM). Hydrogen bonds and van der Waals interactions are the key interactions in the complexes. The results of MD simulations indicate that the introduction of ILs has a prominent effect on the interaction between the solvent molecules, especially on reducing the number of hydrogen bonds among the solvent molecules. The radial distribution function (RDF) reveals that the interaction between the cation and solvent molecules will increase while the concentration of ILs increases. This paper provides important information for understanding the role of ILs in the separation of the azeotropic system, which is valuable to the development of new entrainers.